EP2055733A1 - Lead - Google Patents
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- Publication number
- EP2055733A1 EP2055733A1 EP07021384A EP07021384A EP2055733A1 EP 2055733 A1 EP2055733 A1 EP 2055733A1 EP 07021384 A EP07021384 A EP 07021384A EP 07021384 A EP07021384 A EP 07021384A EP 2055733 A1 EP2055733 A1 EP 2055733A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- wax
- weight
- mine according
- mine
- mines
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 fatty acid salt Chemical class 0.000 claims abstract description 13
- 229920000098 polyolefin Polymers 0.000 claims abstract description 12
- 239000000945 filler Substances 0.000 claims abstract description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 3
- 239000000194 fatty acid Substances 0.000 claims abstract description 3
- 229930195729 fatty acid Natural products 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000049 pigment Substances 0.000 claims description 13
- 239000000314 lubricant Substances 0.000 claims description 6
- 239000005995 Aluminium silicate Substances 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000000454 talc Substances 0.000 claims description 4
- 229910052623 talc Inorganic materials 0.000 claims description 4
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 238000005065 mining Methods 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 claims 2
- 239000004615 ingredient Substances 0.000 claims 1
- 229920005606 polypropylene copolymer Polymers 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- 239000012463 white pigment Substances 0.000 abstract 1
- 239000001993 wax Substances 0.000 description 34
- 238000012937 correction Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 8
- 235000010215 titanium dioxide Nutrition 0.000 description 7
- 239000002989 correction material Substances 0.000 description 6
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 4
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000013039 cover film Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 235000019359 magnesium stearate Nutrition 0.000 description 3
- 235000012222 talc Nutrition 0.000 description 3
- WCOXQTXVACYMLM-UHFFFAOYSA-N 2,3-bis(12-hydroxyoctadecanoyloxy)propyl 12-hydroxyoctadecanoate Chemical compound CCCCCCC(O)CCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCC(O)CCCCCC)COC(=O)CCCCCCCCCCC(O)CCCCCC WCOXQTXVACYMLM-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 235000013799 ultramarine blue Nutrition 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- 241000533901 Narcissus papyraceus Species 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000004164 Wax ester Substances 0.000 description 1
- 230000035508 accumulation Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012182 japan wax Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- 239000001053 orange pigment Substances 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 235000019386 wax ester Nutrition 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
- B43K—IMPLEMENTS FOR WRITING OR DRAWING
- B43K19/00—Non-propelling pencils; Styles; Crayons; Chalks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
- B43L—ARTICLES FOR WRITING OR DRAWING UPON; WRITING OR DRAWING AIDS; ACCESSORIES FOR WRITING OR DRAWING
- B43L19/00—Erasers, rubbers, or erasing devices; Holders therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
- B43L—ARTICLES FOR WRITING OR DRAWING UPON; WRITING OR DRAWING AIDS; ACCESSORIES FOR WRITING OR DRAWING
- B43L19/00—Erasers, rubbers, or erasing devices; Holders therefor
- B43L19/0056—Holders for erasers
- B43L19/0068—Hand-held holders
- B43L19/0075—Hand-held holders of the pencil type
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D13/00—Pencil-leads; Crayon compositions; Chalk compositions
Definitions
- the invention relates to a mine and equipped with such a mine pin.
- the liquids usually contain, in addition to titanium dioxide, which is mainly responsible for the coverage, an organic solvent or water, which is mixed with minor additions of organic solvents, and additives.
- the correction fluids stored in containers are usually applied to the substrate by means of application elements, such as brushes or sponges, which are fixed to a container closure, such as a screw cap.
- application elements such as brushes or sponges
- Machturban is further that the liquids, especially if the container is open for a long time in use, dry relatively quickly and then difficult to distribute on the surface or result in too thick orders. Furthermore, the liquids, especially those based on water, have the property that they dissolve certain dyes, so that the dye of a covered lettering discolors the cover film formed with the liquid. Finally, solvent emissions and, in particular, the associated odor nuisance of the user are disadvantageous.
- containers are used in the form of a writing instrument, which are indeed improved in terms of handling, but bring about other disadvantages.
- the devices have an application tip that delivers correction fluid when pressure is applied to the flexibly held container.
- the application tips dry out very quickly after removal of a seal that seals them during storage and transport, in particular in the event of only sporadic use.
- such devices are relatively expensive to manufacture, especially because of their complex application tip and therefore expensive.
- the disadvantages associated with the aforementioned correction fluids are avoided with application devices that work with correction tapes.
- the tapes have a filler and pigments such as titanium white-containing topcoat and can be unrolled using a complicated rolling mechanism on the surface, the topcoat adheres to the surface. Although this results in a homogeneous and smooth cover film, but only in a straight unwinding direction. In a curved rolling track, wrinkles occur on the concave sides of the cover film due to accumulations of material. In addition, the rolling mechanism is prone to failure. Thus, the correction tapes can break, making the entire device unusable. In addition, the existing rolling machines tend in many cases to block in the application. It is also difficult to make accurate corrections. Some of the cover films applied tend to yellow after several weeks.
- the object of the invention is to enable a correction of the type mentioned without the mentioned disadvantages.
- the invention was initially based on the finding that a mine with a conventional, crayons corresponding consistency could serve as a basis, if these opaque pigments, for example, white pigments such as TiO 2 , ZnO, Mg0 or lithopone contains.
- Lithopone is a mixture or co-precipitate of ZnS and BaSO 4 . It was found that in conventional mines, especially in wax mines, which appeared to be the most promising in terms of their smear behavior, despite high proportions of color pigments, no comprehensive smears on paper documents could be produced. Also, variation of the conventional wax components or fillers contained in the lead mass did not succeed.
- the opaque jobs are overwritable with conventional writing instruments.
- whiteness refers to the (white) appearance of a white coating. It is defined as the reflectance of a white surface compared to, for example, a white standard, and can be determined by means of a spectrophotometer. For tinting a white hue small amounts of blue dye or pigment can be used such. B. ultramarine blue. It is also possible to produce colored mines. For example, for corrections on yellow writing paper, the desired correction solid refill may be colored or tinted with yellow or orange pigments.
- polyolefin waxes with melting ranges between about 50 ° C and 130 ° C are suitable, in particular polyolefin waxes from the group polyethylene wax (CAS 9002-88-4), polypropylene wax (CAS 9003-07-0), propylene-ethylene copolymer wax (9003-07-0), PP copolymer wax (CAS 31069-12-2), ethylene-1-propene copolymer (CAS 9010-79-1), or ethylene-1-propene polymer (CAS 9003-07-0), each alone or in mixtures in question.
- polyethylene wax, polypropylene wax and propylene-ethylene copolymer wax with which particularly well-covering mines can be produced. The orders containing the last two waxes can be overridden particularly well.
- the smear behavior and, to a certain extent, the consistency of the mines can be reduced by the usual waxy and waxy components such as soft waxes based on fatty and soft wax acids such as castor oil, fatty and soft wax glycerides, wax alcohols, wax esters, long-chain branched and unbranched hydrocarbons , hardened waxes, so for example esters of montan acids, stearic acid, palmitic acid, castor wax and paraffin wax vary within wide limits.
- Lubricants are also to be mentioned in this regard, which, in particular, ensure that when the mine is being scraped off on a base, a sufficient amount of ground mass remains adherent, which is important for the opacity of the jobs.
- Lubricants which are customary in wax minerals fatty acid salts such as calcium stearate, magnesium stearate and zinc stearate in a proportion of 3 wt.% To 25 wt.% are included.
- Wachsminen of the type in question are water insoluble.
- a water solubility can be effected by the addition of emulsifiers, which also recommends the use of water-soluble lubricants such as sodium stearate.
- wax mines are also to be understood as those mines containing a small proportion of a water-swellable binder such as sodium carboxymethylcellulose.
- fillers Another important part of the mines are fillers. These have a positive effect on the smear behavior by They counteract solidification of the mine by hard waxes, especially polyolefin waxes.
- inorganic filler particles in particular calcium carbonate, mica, kaolin, soapstone and talcum, in each case alone or in admixture with another of the stated fillers are suitable.
- Below a filler content of 15% by weight, the mines are generally too hard, which means that too little material can be spread on a substrate. Above 30% by weight of fillers, there is a risk that a cohesion of the lead mass sufficient for easy handling of the lead will no longer exist, so that, for example, the leads break off when pressed against a base.
- the exemplary embodiments are mining masses for white correction mines, in the case of examples 2 and 3 ultramarine blue being included for tinting.
- the starting materials are mixed with mixers or kneaders and the resulting lead mass is formed into mines with a diameter of 6 mm using an extruder or an extruder.
- Examples 1-3 show significantly better results in terms of hiding power than conventional white colored pencil lead mines (WR 1). The results are even slightly better than with commercially available correction fluids.
- the reference mine showed only poor hiding power. Since the reference mine and the inventive mines each have a comparable wax-based lead mass and comparable white pigments, it is clear that the cause of the significantly improved hiding power are the polyolefin waxes.
- Example 4 talc 20.00% by weight zinc stearate 5.00% by weight zinc oxide 35.00% by weight Pigment Yellow 81 (CI 21127) 0.50% by weight Polyethylene wax 20.00% by weight Paraffin Wax (Melting range 60-65 ° C) 19.50% by weight
- the lead mass is colored yellow and is particularly suitable for the production of thicker mines, such as high-coverage wax crayons with a diameter of 12 mm.
- the preparation is carried out according to Example 1 to 3, wherein the mines are sharpened before use. From this example, it is clear that a mine according to the invention can be used not only as a correction mine but also for painting purposes, either in the form of crayons or in coated form.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
Die Erfindung betrifft eine Mine und einen mit einer solchen Mine ausgestatteten Stift. Seit langer Zeit ist es bekannt, Linien oder Flächen auf Zeichen- Mal- und Schreibuntergründen, beispielsweise auf weißem Papier, mit Hilfe von Korrekturflüssigkeiten zu überdecken, um etwa Fehler in Texten oder Zeichnungen zu korrigieren bzw. zu retuschieren. Die Flüssigkeiten enthalten üblicherweise neben Titandioxid, das hauptsächlich für die Überdeckung verantwortlich ist, ein organisches Lösemittel oder Wasser, das mit geringfügigen Zusätzen von organischen Lösemitteln versetzt ist, sowie Additive. Die in Behältern aufbewahrten Korrekturflüssigkeiten werden meist mit Hilfe von Applikationselementen wie Pinseln oder Schwämmchen auf die Unterlage aufgetragen, die an einem Behälterverschluss, etwa einer Schraubkappe fixiert sind. Nachteilig dabei ist zunächst, dass mit dem Applikationselement oft mehr Flüssigkeit aus dem Behälter entnommen wird, als zur Korrektur benötigt wird oder dass Flüssigkeit vom Applikationselement abtropft. Machteilig ist weiterhin, dass die Flüssigkeiten, insbesondere wenn der Behälter beim Gebrauch längere Zeit geöffnet ist, relativ schnell eintrocken und dann schwer auf der Unterlage zu verteilen sind oder zu dicke Aufträge ergeben. Weiterhin haben die Flüssigkeiten, insbesondere solche auf Wasserbasis, die Eigenschaft, dass sie bestimmte Farbstoffe auflösen, so dass der Farbstoff einer überdeckten Beschriftung den mit der Flüssigkeit erzeugten Deckfilm verfärbt. Nachteilig sind schließlich Lösemittelemissionen und besonders die damit verbundene Geruchsbelästigung des Verwenders.The invention relates to a mine and equipped with such a mine pin. For a long time, it has been known to cover lines or areas on drawing and writing surfaces, for example on white paper, with the aid of correction fluids in order to correct or retouch errors in texts or drawings, for example. The liquids usually contain, in addition to titanium dioxide, which is mainly responsible for the coverage, an organic solvent or water, which is mixed with minor additions of organic solvents, and additives. The correction fluids stored in containers are usually applied to the substrate by means of application elements, such as brushes or sponges, which are fixed to a container closure, such as a screw cap. The disadvantage here is, first, that often more liquid is removed from the container with the application element than is required for correction or that liquid drips off the application element. Machteilig is further that the liquids, especially if the container is open for a long time in use, dry relatively quickly and then difficult to distribute on the surface or result in too thick orders. Furthermore, the liquids, especially those based on water, have the property that they dissolve certain dyes, so that the dye of a covered lettering discolors the cover film formed with the liquid. Finally, solvent emissions and, in particular, the associated odor nuisance of the user are disadvantageous.
Vielfach werden Behälter in der Form eines Schreibgerätes verwendet, die zwar im Hinblick auf die Handhabung verbessert sind, dafür aber andere Nachteile mit sich bringen. Die Geräte weisen eine Applikationsspitze auf, die etwa bei Druck auf den flexibel gehaltenen Behälter Korrekturflüssigkeit abgibt. Trotz mechanischer Abdichtungen etwa in Form einer Verschlusskugel trocknen die Applikationsspitzen nach Entfernung einer sie während Lagerung und Transport abdichtenden Versiegelung insbesondere bei nur sporadischem Gebrauch sehr schnell aus. Außerdem sind derartige Geräte vor allem wegen ihrer aufwändigen Applikationsspitze relativ aufwändig in der Herstellung und daher teuer.In many cases containers are used in the form of a writing instrument, which are indeed improved in terms of handling, but bring about other disadvantages. The devices have an application tip that delivers correction fluid when pressure is applied to the flexibly held container. Despite mechanical seals, for example in the form of a closure ball, the application tips dry out very quickly after removal of a seal that seals them during storage and transport, in particular in the event of only sporadic use. In addition, such devices are relatively expensive to manufacture, especially because of their complex application tip and therefore expensive.
Die mit den genannten Korrekturflüssigkeiten verbundenen Nachteile werden mit Applikationsgeräten vermieden, die mit Korrekturbändern arbeiten. Die Bänder weisen eine Füllstoffe und Pigmente wie Titanweiß enthaltende Deckbeschichtung auf und sind mit Hilfe einer komplizierten Abrollmechanik auf der Unterlage abrollbar, wobei die Deckbeschichtung an der Unterlage haften bleibt. Dabei entsteht zwar ein homogener und glatter Deckfilm, aber nur bei geradliniger Abrollrichtung. Bei einer gekrümmten Abrollbahn entstehen an den Konkavseiten des Deckfilms aufgrund von Materialanhäufungen Falten. Außerdem ist die Abrollmechanik störanfällig. So können die Korrekturbänder reißen, wodurch das gesamte Gerät unbrauchbar wird. Außerdem neigen die vorhandenen Abroll-Mechaniken in vielen Fällen dazu, bei der Applikation zu blockieren. Auch ist es schwer möglich genaue Korrekturen vorzunehmen. Manche der aufgetragenen Deckfilme neigen nach mehreren Wochen dazu, zu vergilben.The disadvantages associated with the aforementioned correction fluids are avoided with application devices that work with correction tapes. The tapes have a filler and pigments such as titanium white-containing topcoat and can be unrolled using a complicated rolling mechanism on the surface, the topcoat adheres to the surface. Although this results in a homogeneous and smooth cover film, but only in a straight unwinding direction. In a curved rolling track, wrinkles occur on the concave sides of the cover film due to accumulations of material. In addition, the rolling mechanism is prone to failure. Thus, the correction tapes can break, making the entire device unusable. In addition, the existing rolling machines tend in many cases to block in the application. It is also difficult to make accurate corrections. Some of the cover films applied tend to yellow after several weeks.
Aufgabe der Erfindung ist es, eine Korrektur der eingangs genannten Art ohne die erwähnten Nachteile zu ermöglichen.The object of the invention is to enable a correction of the type mentioned without the mentioned disadvantages.
Diese Aufgabe wird durch eine Mine nach Anspruch 1 bzw. ein eine solche Mine enthaltendes Schreibgerät nach Anspruch 12 gelöst.This object is achieved by a mine according to claim 1 or a writing instrument containing such a mine according to claim 12.
Der Erfindung lag dabei zunächst die Erkenntnis zugrunde, dass eine Mine mit einer herkömmlichen, Buntstiften entsprechenden Konsistenz als Grundlage dienen könnte, wenn diese deckende Pigmente, beispielsweise weiße Pigmente wie TiO2, ZnO, Mg0 oder Lithopone enthält. Lithopone ist eine Mischung bzw. ein Co-Präzipität aus ZnS und BaSO4. Dabei zeigte sich, dass bei herkömmlichen Minen, insbesondere bei Wachsminen, die hinsichtlich ihres Abstrichverhaltens am erfolgversprechendsten schienen, trotz hoher Anteile an Farbpigmenten keine deckenden Abstriche auf Papierunterlagen erzeugt werden konnten. Auch führte eine Variation der herkömmlichen Wachsbestandteile oder in der Minenmasse enthaltener Füllstoffe zu keinem Erfolg. Völlig überraschend war dann, dass mit Wachsminen mit 1 Gew.% bis 30 Gew.% wenigstens eines Polyolefinwachses bei einem Anteil an Pigmenten, insbesondere von Weißpigmenten wie Titanweiß oder Lithopone, von 30 Gew.% bis 70 Gew.% deckende Abstriche vor allem auf Papierunterlagen erzeugt werden können. Die Abstriche weisen eine hohe Deckkraft auf, sind dauerhaft, lösen den Farbstoff von damit überdeckten Beschriftungen nicht an, und sind außerdem lösemittel- und daher geruchsfrei. Außerdem sind die Minen ohne Einbuße ihrer Gebrauchseigenschaften lange lagerfähig. Eine Mine und ein eine Mine enthaltendes Schreibgerät, etwa ein holz- oder kunststoffummantelter Stift, sind sehr einfach und effizient handhabbar. Es lassen sich damit sowohl punktgenaue Korrekturen vornehmen als auch größere Flächenbereiche einer Unterlage mit einem hochdeckenden, mit herkömmlichen Korrekturflüssigkeiten vergleichbaren Auftrag versehen. Die deckenden Aufträge sind mit herkömmlichen Schreibgeräten überschreibbar. Im Falle eines weißen Untergrunds ergeben die bereits oben erwähnten Weißpigmente Aufträge mit einem hohen Weißgrad. Mit Weißgrad wird das (weiße) Aussehen einer weißen Beschichtung bezeichnet. Er ist als das Reflexionsvermögen einer weißen Oberfläche im Vergleich etwa zu einem Weißstandard definiert und kann mit Hilfe eines Spektralphotometers bestimmt werden. Zur Abtönung eines Weißfarbtons können geringe Mengen an Blaufarbstoff oder -Pigment zum Einsatz kommen wie z. B. Ultramarinblau. Es ist auch möglich farbige Minen herzustellen. Beispielsweise für Korrekturen auf gelbem Schreibpapier kann die gewünschte Korrekturfeststoffmine mit Gelb- oder Orange-Pigmenten eingefärbt bzw. getönt sein.The invention was initially based on the finding that a mine with a conventional, crayons corresponding consistency could serve as a basis, if these opaque pigments, for example, white pigments such as TiO 2 , ZnO, Mg0 or lithopone contains. Lithopone is a mixture or co-precipitate of ZnS and BaSO 4 . It was found that in conventional mines, especially in wax mines, which appeared to be the most promising in terms of their smear behavior, despite high proportions of color pigments, no comprehensive smears on paper documents could be produced. Also, variation of the conventional wax components or fillers contained in the lead mass did not succeed. Completely surprising was then that with wax mines with 1 wt.% To 30 wt.% Of at least one polyolefin wax with a proportion of pigments, in particular white pigments such as titanium white or lithopone, from 30 wt.% To 70 wt.% Covering smears mainly on Paper documents can be generated. The smears have a high opacity, are durable, do not dissolve the dye from overlapping labels, and are also solvent-free and therefore odor-free. In addition, the mines can be stored for long periods without any loss in their performance characteristics. A mine and a writing instrument containing a refill, such as a wood- or plastic-coated pencil, are very easy and efficient to handle. It can thus make both precise corrections as well as larger Surface areas of a pad provided with a high opacity, comparable with conventional correction liquids order. The opaque jobs are overwritable with conventional writing instruments. In the case of a white background, the white pigments already mentioned above give high whiteness jobs. Whiteness refers to the (white) appearance of a white coating. It is defined as the reflectance of a white surface compared to, for example, a white standard, and can be determined by means of a spectrophotometer. For tinting a white hue small amounts of blue dye or pigment can be used such. B. ultramarine blue. It is also possible to produce colored mines. For example, for corrections on yellow writing paper, the desired correction solid refill may be colored or tinted with yellow or orange pigments.
Ein gutes Deckverhalten wird erzielt, wenn die Minen den oben angegebenen Anteil an Polyolefinwachs enthalten. Unterhalb von 1 Gew.% ist ein deckender Effekt von Polyolefinwachsen nicht mehr zu beobachten. Ab einem Gehalt ab 5 Gew. % wird eine gute Deckung erreicht, wobei hinsichtlich des Anteils an Pigmenten ein relativ großer Spielraum besteht. Ein Anteil von mehr als 30 Gew.% Polyolefinwachs bringt keine weitere Erhöhung der Deckkraft. Auch wird bei hohen Gehalten an Polyolefinwachsen die Mine relativ fest, wodurch sich das Abstrichverhalten der Mine verschlechtert. Grundsätzlich sind Polyolefinwachse mit Schmelzbereichen zwischen etwa 50 °C und 130 °C geeignet, wobei vor allem Polyolefinwachse aus der Gruppe Polyethylenwachs (CAS 9002-88-4), Polypropylenwachs (CAS 9003-07-0), Propylen-Ethylen-Copolymer-Wachs (9003-07-0), PP-Copolymer-Wachs (CAS 31069-12-2), Ethylene-1-propen Copolymer (CAS 9010-79-1), oder Ethylen-1-propen-polymer (CAS 9003-07-0), jeweils alleine oder in Mischungen in Frage. Hervorzuheben sind dabei Polyethylenwachs, Polypropylenwachs und Propylen-Ethylen-Copolymer-Wachs, mit denen besonders gut deckende Minen herstellbar sind. Die beiden letztgenannten Wachse enthaltende Aufträge sind besonders gut überschreibbar.Good coverage is achieved when the mines contain the above-stated level of polyolefin wax. Below 1% by weight, a covering effect of polyolefin waxes is no longer observed. From a content of 5% by weight, a good coverage is achieved, with respect to the proportion of pigments, a relatively large margin exists. A proportion of more than 30 wt.% Polyolefinwachs brings no further increase in opacity. Also, at high levels of polyolefin waxes, the lead becomes relatively solid, thereby degrading the smear behavior of the lead. In principle, polyolefin waxes with melting ranges between about 50 ° C and 130 ° C are suitable, in particular polyolefin waxes from the group polyethylene wax (CAS 9002-88-4), polypropylene wax (CAS 9003-07-0), propylene-ethylene copolymer wax (9003-07-0), PP copolymer wax (CAS 31069-12-2), ethylene-1-propene copolymer (CAS 9010-79-1), or ethylene-1-propene polymer (CAS 9003-07-0), each alone or in mixtures in question. Worth mentioning are polyethylene wax, polypropylene wax and propylene-ethylene copolymer wax, with which particularly well-covering mines can be produced. The orders containing the last two waxes can be overridden particularly well.
Das Abstrichverhalten sowie in gewissem Rahmen auch die Konsistenz der Minen lassen sich durch die bei Wachsminen üblichen wachs- und fettartigen Bestandteile wie Weichwachse auf der Basis von Fett- und Weichwachssäuren wie Castoröl, Fett- und Weichwachsglyceride, Wachsalkohole, Wachsester, langkettige verzweigte und unverzweigte Kohlenwasserstoffe, gehärtete Wachse, also beispielsweise Ester von Montansäuren, Stearinsäure, Palmitinsäure, Castorwachs und Paraffinwachs in weiten Bereichen variieren. In dieser Hinsicht sind auch Gleitmittel zu nennen, die insbesondere gewährleisten, dass beim Abstreichen der Mine auf einer Unterlage eine ausreichende Menge an Minenmasse haften bleibt, was für die Deckfähigkeit der Aufträge wichtig ist. Als Gleitmittel sind die bei Wachsminen üblichen Fettsäuresalze wie Calciumstearat, Magnesiumstearat und Zinkstearat mit einem Anteil von 3 Gew.% bis 25 Gew.% enthalten. Wachsminen der in Rede stehenden Art sind wasserunlöslich. Eine Wasserlöslichkeit kann aber durch Zusatz von Emulgatoren bewirkt werden, wobei sich dabei auch der Einsatz wasserlöslicher Gleitmittel wie Natriumstearat empfiehlt. Unter dem Begriff Wachsminen sind auch solche Minen zu verstehen, die einen geringen Anteil eines wasserquellbaren Bindemittels wie Natriumcarboxymethylcellulose enthalten.The smear behavior and, to a certain extent, the consistency of the mines can be reduced by the usual waxy and waxy components such as soft waxes based on fatty and soft wax acids such as castor oil, fatty and soft wax glycerides, wax alcohols, wax esters, long-chain branched and unbranched hydrocarbons , hardened waxes, so for example esters of montan acids, stearic acid, palmitic acid, castor wax and paraffin wax vary within wide limits. Lubricants are also to be mentioned in this regard, which, in particular, ensure that when the mine is being scraped off on a base, a sufficient amount of ground mass remains adherent, which is important for the opacity of the jobs. Lubricants which are customary in wax minerals fatty acid salts such as calcium stearate, magnesium stearate and zinc stearate in a proportion of 3 wt.% To 25 wt.% Are included. Wachsminen of the type in question are water insoluble. However, a water solubility can be effected by the addition of emulsifiers, which also recommends the use of water-soluble lubricants such as sodium stearate. The term wax mines are also to be understood as those mines containing a small proportion of a water-swellable binder such as sodium carboxymethylcellulose.
Ein weiterer wichtiger Bestandteil der Minen sind Füllstoffe. Diese wirken sich positiv auf das Abstrichverhalten aus, indem sie einer Verfestigung der Mine durch harte Wachse, vor allem Polyolefinwachse, entgegenwirken. Es kommen vor allem anorganische Füllstoffpartikel, insbesondere Calciumcarbonat, Glimmer, Kaolin, Specksteinmehl und Talkum, jeweils alleine oder in Mischung mit einem anderen der genannten Füllstoffe in Frage. Unterhalb eines Füllstoffanteils von 15 Gew.% sind die Minen in der Regel zu hart, wodurch sich zu wenig Material auf einer Unterlage abstreichen lässt. Oberhalb von 30 Gew.% Füllstoffen besteht die Gefahr, dass ein für eine problemlose Handhabung der Mine ausreichender Zusammenhalt der Minenmasse nicht mehr gegeben ist, so dass z.B. die Minen beim Andrücken an eine Unterlage abbrechen.Another important part of the mines are fillers. These have a positive effect on the smear behavior by They counteract solidification of the mine by hard waxes, especially polyolefin waxes. In particular, inorganic filler particles, in particular calcium carbonate, mica, kaolin, soapstone and talcum, in each case alone or in admixture with another of the stated fillers are suitable. Below a filler content of 15% by weight, the mines are generally too hard, which means that too little material can be spread on a substrate. Above 30% by weight of fillers, there is a risk that a cohesion of the lead mass sufficient for easy handling of the lead will no longer exist, so that, for example, the leads break off when pressed against a base.
Es handelt sich bei den Ausführungsbeispielen um Minenmassen für weiße Korrekturminen, wobei im Falle von Beispiel 2 und 3 Ultramarinblau zur Abtönung enthalten ist. Die Ausgangsstoffe werden mit Mischern oder Knetern vermengt und die so erhaltene Minenmasse mit einer Strangpresse oder einem Extruder zu Minen mit einem Durchmesser von 6 mm ausgeformt.The exemplary embodiments are mining masses for white correction mines, in the case of examples 2 and 3 ultramarine blue being included for tinting. The starting materials are mixed with mixers or kneaders and the resulting lead mass is formed into mines with a diameter of 6 mm using an extruder or an extruder.
Es handelt sich hier um eine herkömmliche Wachsminenmasse für weiße Minen.It is a traditional wax mine mass for white mines.
Minen entsprechend den Beispielen 1 bis 3 wurden im Vergleich zu einer handelsüblichen Korrektur-flüssigkeit und einer dem Vergleichsbeispiel entsprechenden Mine mit einem Durchmesser von 4 mm (Referenzbeispiel WR1) getestet. Hierzu wurden vollständig schwarze Felder mit einem Tintenstrahldrucker HP DeskJet 990 CXi auf weißem Papier erzeugt. Jeweils ein Feld wurde mit dem Referenzfarbstift WR 1, einer handelsüblichen Korrekturflüssigkeit sowie den Minen gemäß den Beispielen 1 - 3 überstrichen.Mines according to Examples 1 to 3 were tested in comparison with a commercially available correction liquid and a mine equivalent to the comparative example with a diameter of 4 mm (Reference Example WR1). For this purpose, completely black fields were created on white paper with an HP DeskJet 990 CXi inkjet printer. In each case a field was overlined with the reference color pencil WR 1, a commercial correction fluid and the mines according to Examples 1-3.
Eine Auswertung der Ergebnisse erfolgte mit dem Farbmessgerät Mercury - Cielab der Firma Datacolor (Dietlikon,CH). Ermittelt wurden hierbei die Weißwerte ΔL gegenüber einem mit dem genannten Drucker erzeugten schwarzen Hintergrund (ΔL = 0).
Aus den so erhaltenen Werten ergibt sich eindeutig, dass die erfindungsgemäßen Minen (Beispiele 1-3) signifikant bessere Ergebnisse in Bezug auf das Deckvermögen aufzeigen, als herkömmliche weiße Farbstiftminen (WR 1). Die Ergebnisse sind sogar geringfügig besser als bei handelsüblichen Korrekturflüssigkeiten. Die Referenzmine zeigte nur ein mangelhaftes Deckvermögen. Da die Referenzmine und die erfindungsgemäßen Minen jeweils eine vergleichbare Minenmasse auf Wachsbasis und vergleichbare Weißpigmente aufweisen, wird deutlich, dass die Ursache für das erheblich verbesserte Deckvermögen die Polyolefinwachse sind.From the values obtained in this way, it is clear that the mines according to the invention (Examples 1-3) show significantly better results in terms of hiding power than conventional white colored pencil lead mines (WR 1). The results are even slightly better than with commercially available correction fluids. The reference mine showed only poor hiding power. Since the reference mine and the inventive mines each have a comparable wax-based lead mass and comparable white pigments, it is clear that the cause of the significantly improved hiding power are the polyolefin waxes.
Beispiel 4:Example 4:
Die Minenmasse ist gelb eingefärbt und eignet sich besonders für die Herstellung von dickeren Minen, etwa von hochdeckenden Wachsmalkreiden mit einem Durchmesser von 12 mm. Die Herstellung erfolgt entsprechend Beispiel 1 bis 3, wobei die Minen vor dem Gebrauch angespitzt werden. An diesem Beispiel wird deutlich, dass eine erfindungsgemäße Mine nicht nur als Korrekturmine sondern auch für Malzwecke, entweder in der Form einer Wachsmalkreide oder in ummantelter Form, verwendet werden kann.The lead mass is colored yellow and is particularly suitable for the production of thicker mines, such as high-coverage wax crayons with a diameter of 12 mm. The preparation is carried out according to Example 1 to 3, wherein the mines are sharpened before use. From this example, it is clear that a mine according to the invention can be used not only as a correction mine but also for painting purposes, either in the form of crayons or in coated form.
Claims (13)
dadurch gekennzeichnet,
dass 5 Gew.% bis 20 Gew. % Polyolefinwachs enthalten sind.Mine according to claim 1,
characterized,
that 5 wt.% To 20 wt.% Polyolefin wax are included.
dadurch gekennzeichnet,
dass 35 Gew.% bis 60 Gew.% Pigmente enthalten sind.Mine according to claim 1 or 2,
characterized,
that 35% by weight to 60% by weight of pigments are contained.
dadurch gekennzeichnet,
dass wenigstens ein Polyolefinwachs aus der Gruppe Polyethylenwachs, Polypropylenwachs, Polyethylen-Polypropylen-Copolymerwachs enthalten ist.Mine according to one of the preceding claims,
characterized,
that at least one polyolefin wax from the group polyethylene wax, polypropylene wax, polyethylene-polypropylene copolymer wax is included.
dadurch gekennzeichnet,
dass sie als Pigment Titanoxid und/oder Lithopone enthält.Mine according to one of the preceding claims,
characterized,
that it contains as pigment titanium oxide and / or lithopone.
dadurch gekennzeichnet,
dass wenigstens ein Füllstoff enthalten ist.Mine according to one of the preceding claims,
characterized,
that at least one filler is included.
dadurch gekennzeichnet, dass Füllstoff mit einem Anteil von 15 Gew.% bis 30 Gew. enthalten ist.Mine according to claim 6,
characterized in that filler is contained in a proportion of 15 wt.% To 30 wt.
gekennzeichnet durch
wenigstens einen Füllstoff aus der Gruppe Kaolin, Calciumcarbonat, Specksteinmehl, Glimmer, Talkum.Mine according to claim 6 or 7,
marked by
at least one filler from the group kaolin, calcium carbonate, soapstone, mica, talc.
dadurch gekennzeichnet, dass wenigstens ein Gleitmittel enthalten ist.Mine according to one of the preceding claims,
characterized in that at least one lubricant is included.
gekennzeichnet durch
einen Anteil an Gleitmittel von 3 bis 25 Gew.%.Mine according to claim 9,
marked by
a lubricant content of 3 to 25% by weight.
dadurch gekennzeichnet, dass ein Fettsäuresalz als Gleitmittel vorhanden ist.Mine according to claim 9 or 10,
characterized in that a fatty acid salt is present as a lubricant.
dadurch gekennzeichnet,
dass wenigstens ein wachs- und/oder fettartiger Bestandteil enthalten ist.Mine according to one of the preceding claims,
characterized,
that at least one waxy and / or fat-like ingredient is included.
dadurch gekennzeichnet,
dass als fettartiger Bestandteil Stearinsäure, Montansäure, Fett- und Weichwachsglycerid, Wachsalkohole, Wachsester, Ester einer Montansäuren, Castoröl und/oder Palmitinsäure enthalten ist.Mine according to claim 12,
characterized,
that as a fat-like part of stearic acid, montanic acid, fat and Weichwachsglycerid, wax alcohols, wax Sester, Ester a montan acids, castor oil and / or palmitic acid is included.
Priority Applications (3)
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AT07021384T ATE467656T1 (en) | 2007-11-02 | 2007-11-02 | MINE |
DE502007003781T DE502007003781D1 (en) | 2007-11-02 | 2007-11-02 | mine |
EP07021384A EP2055733B1 (en) | 2007-11-02 | 2007-11-02 | Lead |
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EP07021384A EP2055733B1 (en) | 2007-11-02 | 2007-11-02 | Lead |
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EP2055733B1 EP2055733B1 (en) | 2010-05-12 |
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AT (1) | ATE467656T1 (en) |
DE (1) | DE502007003781D1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2015078556A1 (en) * | 2013-11-29 | 2015-06-04 | J.S. Staedtler Gmbh & Co. Kg | Lead refill for writing, drawing and/or painting devices and method for the production thereof |
US10308063B2 (en) | 2014-12-17 | 2019-06-04 | Conte | Paper pencil lead |
US10711150B2 (en) | 2017-07-12 | 2020-07-14 | Crayola Llc | Color development writing compositions and writing instruments |
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GB1212469A (en) * | 1968-03-29 | 1970-11-18 | Padowicz M | Pencil leads, crayons and like marking substances |
US4212676A (en) * | 1978-02-22 | 1980-07-15 | Sakura Color Products Corporation | Compositions for solid writing materials and writing implements |
DD239213A1 (en) * | 1985-07-10 | 1986-09-17 | Varia Chem Fab Muegeln Veb | WAX PLAST COMPOSITIONS FOR WAX COLORS |
JPH0532098A (en) * | 1991-07-30 | 1993-02-09 | Pentel Kk | Solid correction tool |
EP0636668A1 (en) * | 1993-07-28 | 1995-02-01 | Sakura Color Products Corporation | Solid drawing composition |
-
2007
- 2007-11-02 DE DE502007003781T patent/DE502007003781D1/en active Active
- 2007-11-02 EP EP07021384A patent/EP2055733B1/en active Active
- 2007-11-02 AT AT07021384T patent/ATE467656T1/en active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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GB1212469A (en) * | 1968-03-29 | 1970-11-18 | Padowicz M | Pencil leads, crayons and like marking substances |
US4212676A (en) * | 1978-02-22 | 1980-07-15 | Sakura Color Products Corporation | Compositions for solid writing materials and writing implements |
DD239213A1 (en) * | 1985-07-10 | 1986-09-17 | Varia Chem Fab Muegeln Veb | WAX PLAST COMPOSITIONS FOR WAX COLORS |
JPH0532098A (en) * | 1991-07-30 | 1993-02-09 | Pentel Kk | Solid correction tool |
EP0636668A1 (en) * | 1993-07-28 | 1995-02-01 | Sakura Color Products Corporation | Solid drawing composition |
Non-Patent Citations (1)
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DATABASE WPI Week 199311, Derwent World Patents Index; AN 1993-088435, XP002471969 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015078556A1 (en) * | 2013-11-29 | 2015-06-04 | J.S. Staedtler Gmbh & Co. Kg | Lead refill for writing, drawing and/or painting devices and method for the production thereof |
US10457826B2 (en) | 2013-11-29 | 2019-10-29 | Staedtler Mars Gmbh & Co. Kg | Lead refill for writing, drawing and/or painting devices and method for the production thereof |
US10308063B2 (en) | 2014-12-17 | 2019-06-04 | Conte | Paper pencil lead |
US10711150B2 (en) | 2017-07-12 | 2020-07-14 | Crayola Llc | Color development writing compositions and writing instruments |
Also Published As
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DE502007003781D1 (en) | 2010-06-24 |
ATE467656T1 (en) | 2010-05-15 |
EP2055733B1 (en) | 2010-05-12 |
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